WO2026017663A1 - Procédé de production efficace d'une composition de polyester solide contenant un additif - Google Patents

Procédé de production efficace d'une composition de polyester solide contenant un additif

Info

Publication number
WO2026017663A1
WO2026017663A1 PCT/EP2025/070179 EP2025070179W WO2026017663A1 WO 2026017663 A1 WO2026017663 A1 WO 2026017663A1 EP 2025070179 W EP2025070179 W EP 2025070179W WO 2026017663 A1 WO2026017663 A1 WO 2026017663A1
Authority
WO
WIPO (PCT)
Prior art keywords
melt
polyester
cyclic ester
additive
devolatilized
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/070179
Other languages
English (en)
Inventor
Ho Ting LUK
Adrian STREHLER
Yingchuan Yu
Luca BARCARO
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sulzer Management AG
Original Assignee
Sulzer Management AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sulzer Management AG filed Critical Sulzer Management AG
Publication of WO2026017663A1 publication Critical patent/WO2026017663A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/80—Component parts, details or accessories; Auxiliary operations
    • B29B7/88—Adding charges, i.e. additives
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B9/00—Making granules
    • B29B9/12—Making granules characterised by structure or composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/005—Processes for mixing polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/201—Pre-melted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
    • C08J2367/04—Polyesters derived from hydroxy carboxylic acids, e.g. lactones

Definitions

  • the present invention relates to a process for producing an additive containing solid polyester composition, such as polylactic acid, polycaprolactone, polyglycolic acid or combinations thereof, from a cyclic ester composition containing at least one cyclic ester, such as a lactone or a cyclic diester.
  • a cyclic ester composition containing at least one cyclic ester, such as a lactone or a cyclic diester.
  • Polyesters are an important family of polymer due to their mechanical and chemical properties suitable in a wide field of applications.
  • Prominent examples for polyesters are polylactones, i.e. homo- and copolymers based on lactone, as well as poly-a-hydroxy acids. These are of particular interest, because they are completely biodegradable and compostable.
  • the technological properties of these polymers come quite close to the properties of non-biodegradable and fossilbased polymers, such as polyethylene, which explains why these polymers are regarded as highly promising substitutes for the latter.
  • polycaprolactone which is derived from a cyclic ester, namely s-caprolactone, which in turn is originated from the intramolecular esterification of hydroxycaproic acid.
  • the classical way of producing caprolactone was via Baeyer-Villiger oxidation of cyclohexanone with peracetic acid coming from acetic acid and hydrogen peroxide.
  • Polycaprolactone finds widespread applications in the production of speciality polyurethanes and is characterized by a good resistance to water, to oil and to solvent.
  • polycaprolactone is used as material for packings or for biomedical articles, such as for drug delivery devices, for adhesives, for synthetic wound dressings and for orthopedic imprints.
  • Other examples for commercially interesting polylactones are polyvalerolactone and polybutyrolactone.
  • Other important examples of polyesters are poly-a-hydroxy acids, which are of particular interest, because they are not only mostly compostable and/or biodegradable, but they can be also obtained from renewable resources. The technological properties of these polymers are distinctively different from polylactone and yet comparable with some other kind of fossil-based polymers making them highly promising substitutes for the latter.
  • polylactic acid and polyglycolic acid are based lactic acid and glycolic acid, respectively, as a-hydroxy acid. Both have a wide range of applications.
  • polylactic acid is used in the biomedical field in chirurgical implants, in films, such as e.g. in packaging, in fibers, such as e.g. for garments, in hygienic articles, in carpets and in disposable plastic products, such as e.g. disposable cutlery or containers.
  • polylactic acid has found wide application in composite materials, such as in fiber-reinforced plastics.
  • polyglycolic acid is widely used in the medical field, for instance as suture material.
  • polyester properties may be roughly adjusted to the desired application by appropriately selecting the monomers and optional comonomers as well as by adjusting appropriate molecular weights, usually a fine tailoring is required by adding one or more additives to the polyester, such as one or more antioxidants, one or more plasticizers, one or more lubricants, one or more anti-hydrolysis agents or the like.
  • polymers such as polyesters
  • additives are added to the polymer during the extrusion.
  • stepwise approaches typically alter the properties of the polyester and impose thermal stress to the polyesters. Specifically, the polymers were cooled, pelletized, remelt again for extrusion and then the same procedures repeat.
  • the homogeneity of the polyester mixture is limited by the quantity of additives, but also the selected extruder or blending equipment, which has to shred the additives and polyester under high shear rate and excessive temperature.
  • the object underlying the present invention is to provide a fast and simple process of producing a polyester composition, which already contains all required additives, from a cyclic ester composition by ring-opening-polymerization of at least one cyclic ester with applying minimal thermal stress to the polyester and without alteration of the properties of the produced polyester.
  • this object is satisfied by providing a process of producing an additive containing solid polyester composition from a cyclic ester composition containing at least one cyclic ester comprising the steps of: a) polymerizing the at least one cyclic ester contained in the cyclic ester composition by ring-opening-polymerization so as to obtain a crude polyester melt, b) devolatilizing the crude polyester melt so as to obtain a gaseous composition and a devolatilized polyester melt and c) post-processing the devolatilized polyester melt so as to obtain a solid polyester composition, wherein at least one additive and at least one solid polyester are fed into an extruder and are mixed, before the so obtained mixture is added before or during step a) into the cyclic ester composition or after step a) into the crude polyester melt or into the devolatilized polyester melt.
  • the process in accordance with the present invention is fast and simple and requires a process plant with less capital expenditures, because it allows - in comparison to prior art processes - to use an extruder with a reduced size or to even skip the use of an extruder during the production of the polyester composition.
  • the process in accordance with the present invention allows to add the at least one additive into the polyester melt in liquid form or in solid form and in particular allows to add heat sensitive additive(s) so that the process in accordance with the present invention is flexible and versatile.
  • the additive addition may be performed under pressure and temperature control and a homogeneous distribution of the additive(s) within the polyester composition is easily possible through mixing with static mixers.
  • the present invention is not particularly limited concerning the kind of the at least cyclic ester contained in the cyclic ester composition. Good results are for instance obtained, when at least one cyclic ester contained in the cyclic ester composition is a lactone. Suitable examples for lactone are those being selected from the group consisting of caprolactone, propiolactone, valerolactone, butyrolactone, decanolactone and arbitrary combinations thereof. Most preferably, the at least one lactone is a caprolactone and in particular s-caprolactone.
  • At least one cyclic ester contained in the cyclic ester composition is a cyclic diester.
  • cyclic diesters are lactide, glycolide or a mixture containing lactide and glycolide.
  • the cyclic ester composition may contain at least one lactone and at least one cyclic diester so as to produce in step a) a copolymer.
  • the cyclic ester composition may contain one or more other cyclic esters, such as trimethylene carbonate, ethylene carbonate and propylene carbonate.
  • the at least one additive is selected from the group consisting of nucleating agents, plasticizers, lubricants, chain extenders, antioxidants, anti-hydrolysis agent and arbitrary combinations thereof.
  • nucleating agent are ethylene-bis-stearamide, talc, calcium carbonate, other inorganic carbonates, kaolin, chalk, clay, and combinations thereof.
  • plasticizers are any organic acid ester, such as acetic acid ester, citric acid ester, lactic acid ester and combinations thereof.
  • organic lubricant are mineral oil and vegetable oils and specific examples of inorganic lubricants are powders, such as graphite and silicones.
  • chain extenders are ethylene carbonate, Joncryl polymeric chain extender, diisocyanate, ethylene glycol, poly glycols and combinations thereof.
  • antioxidant are phenolic antioxidant stabilizers, which can be sterically hindered, or primary phenolic stabilizers.
  • Example of sterically hindered phenolic antioxidant are pentaerythritol tetrakis(3-(3,5-di-tert-butyl-4- hydroxyphenyl)propionate) (Irganox 1010), while primary hindered phenolic antiox- ident can be octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox 1076). Other examples are such as Irganox 245, Irganox 1098, and combinations thereof.
  • Specific example of anti-hydrolysis agent are those from the family of carbodiimide such as Stabaxol 1 , P, P LF, P100, P110, P200, and combinations thereof.
  • At least one additive is added into the cyclic ester composition before or during step a).
  • At least one additive is added into the crude polyester melt between steps a) and b), i.e. after completion of the ring-opening-polymerization and before the start of the devolatilization.
  • This embodiment is particularly advantageous, when the added additive has any advantageous influence on the devolatilization, for instance by protecting the polyester during the devolatilization against thermal stress or even thermal degradation.
  • At least one additive is added into the devolatilized polyester melt obtained in step b).
  • This embodiment is particularly advantageous, when the added additive is heat sensitive and thus would be deteriorated or even decomposed during the prior devolatilization.
  • At least one additive is added into the crude polyester melt between steps a) and b), whereas at least one other additive is added into the devolatilized polyester melt obtained in step b), or at least one additive is added into the cyclic ester composition before or during step a), whereas at least one other additive is added into the devolatilized polyester melt obtained in step b) or into the crude polyester melt between steps a) and b).
  • at least one additive is into the cyclic ester composition before or during step a)
  • at least one other additive is added into the crude polyester melt between steps a) and b) and at least one other additive is added into the devolatilized polyester melt obtained in step b).
  • a portion of at least one additive is added into the into the cyclic ester composition between steps a) and b), whereas another portion of the same additive is added into the devolatilized polyester melt obtained in step b) and/or into the crude polyester melt before or during step a).
  • At least one additive and preferably a liquid additive is added in a static mixer into the devolatilized polyester melt obtained in step b) or added upstream of a static mixer into the devolatilized polyester melt obtained in step b) before the so obtained blend is led into a static mixer, wherein the mixture obtained in the static mixer is then solidified by leading it through a melt cooler and optionally by thereafter pelletizing it. Because the mixing of the devolatilized polyester melt and of the at least one additive are conducted in liquid phase within the static mixer in liquid phase, the homogeneity and interaction between the at least one additive and the polymer are maximized compared to a single-step extrusion of both components.
  • Liquid means in this connection that the additive is at ambient temperature and at ambient pressure liquid.
  • the liquid additive may be added into the devolatilized polyester melt in the static mixer or upstream thereof through a dosing pump, such as through a gear pump.
  • the mixture obtained in the static mixer is then solidified by leading it through a melt cooler and optionally by thereafter pelletizing it, which means that the solidification of the mixture is either achieved in the melt cooler or in the pelletizer, wherein in the latter case the mixture is only pre-cooled in the melt cooler, but leaves the melt cooler still as liquid or melt, respectively.
  • Static mixer means in this connection any mixer, which does not comprise any moving part and in particular no rotating part.
  • Control valves and bended pipes are not considered as static mixer in this case because the polymer melt behaves laminar.
  • Static mixers usually produce a mixing effect by generating a turbulent flow due to static, i.e. non-moving elements, such as plates, bars, crossbars, baffles, helically formed deflection means, grids and the like.
  • Suitable examples for static mixers are x- type static mixers, spiral/helical-type static mixers, quattro-type static mixers, baffle plate-type static mixers, turbulator strips-type static mixers and any combination of two or more of the abovementioned mixer types.
  • X-type static mixers comprise deflection means in the form of bars, crossbars, plates or the like having in a plan view and/or side view and/or cross-sectional view a x-like form.
  • Such x-type static mixers are described for instance in WO 2010/066457 A1 , EP 1 206 962 A1 , EP 2 158 027 B1 and EP 0 655275 B1 and are commercially available from Sulzer Chemtech Ltd, Winterthur, Switzerland under the tradenames SMX, SMXL and SMX plus as well as from Fluitec, Neftenbach, Switzerland under the tradename CSE-X.
  • Spiral/helical-type static mixers have a helically formed deflection means and are described for instance in US 3,743,250 A, whereas quattro-type static mixers comprise deflection means forming chamber-like mixing sections and are described for instance in EP 2 548 634 B1 and in EP 0 815 929 B1.
  • At least one additive and preferably at least one solid additive is fed into an extruder and is molten therein, before the at least one molten additive is transferred to a static mixer and added therein into the devolatilized polyester melt obtained in step b) or is added upstream of a static mixer into the devolatilized polyester melt obtained in step b) before the so obtained blend is led into a static mixer, wherein the mixture obtained in the static mixer is then solidified by leading it through a melt cooler and optionally by thereafter pelletizing it.
  • Solid means in this connection that the additive is at ambient temperature and at ambient pressure solid.
  • the at least one liquid additive may be added into the devolatilized polyester melt in the static mixer or upstream thereof through a dosing pump, such as through a gear pump.
  • a dosing pump such as through a gear pump.
  • the mixture obtained in the static mixer is then solidified by leading it through a melt cooler and optionally by thereafter pelletizing it, which means that the solidification of the mixture is either achieved in the melt cooler or in the pelletizer, wherein in the latter case the mixture is only pre-cooled in the melt cooler, but leaves the melt cooler still as liquid or melt, respectively.
  • At least i) one additive and preferably at least one solid additive and ii) at least one solid polyester, for instance in the form of pellets, are fed into an extruder and are mixed as well as molten therein, before the so obtained melt is transferred to a static mixer and added therein into the devolatilized polyester melt obtained in step b) or is added upstream of a static mixer into the devolatilized polyester melt obtained in step b) before the so obtained blend is led into a static mixer, wherein the mixture obtained in the static mixer is then solidified by leading it through a melt cooler and optionally by thereafter pelletizing it.
  • This third particularly preferred embodiment is advantageous compared to the aforementioned second particularly preferred embodiment, when the at least one solid additive cannot be molten under reasonable temperature of in particular less than 250°C and thus requires a pre-dispersion in a polymer melt through extrusion.
  • the third particularly preferred embodiment is particularly advantageous, when the degradation temperature of the at least one solid additive is lower than its melting point.
  • the third particularly preferred embodiment is especially suitable for heat-sensitive solid additive(s), because it assures an extended mixing time, namely as sum of the mixing time within the extruder and the mixing time within the static mixer.
  • the solid polyester used in this embodiment of the present invention may be the same or a different to that obtained in the ring-opening-polymerization step a).
  • the obtained polyester pellets is thereafter fed into an extruder and is molten therein, which covers the variant that the at least portion of the obtained polyester pellets is immediately or within short term after having been pelletized fed into the extruder as well as the variant that the obtained polyester pellets are first stored for days, weeks or even months, before at least a portion thereof is fed into the extruder.
  • This fourth particularly preferred embodiment has the same advantages as the aforementioned third particularly preferred embodiment.
  • the solid polyester used in this embodiment of the present invention may be the same or a different to that obtained in the ring-opening-polymerization step a).
  • the devolatilized polyester melt obtained in step b) is led through a static mixer and then through a melt cooler, in which the devolatilized polyester melt obtained in step b) is cooled, but not solidified, wherein i) at least one additive and preferably at least one solid additive and ii) at least one solid polyester are fed into an extruder and are mixed as well as molten therein, before the so obtained melt is added to the cooled devolatilized polyester melt, before the so obtained mixture is solidified.
  • the solid polyester used in this embodiment of the present invention may be the same or a different to that obtained in the ring-opening- polymerization step a).
  • this embodiment is particularly suitable for heat sensible additive(s), which may be processed in the extruder at a comparable low temperature and are added to the already cooled devolatilized polyester melt, wherein the residence time of the additive in the devolatilized polyester melt is comparably short, since it is not led through a static mixer.
  • the devolatilized polyester melt obtained in step b) is led through a melt cooler, in which the devolatilized polyester melt obtained in step b) is cooled, but not solidified, wherein i) at least one additive and preferably at least one solid additive and ii) at least one solid polyester are fed into an extruder and are mixed as well as molten therein, before the so obtained melt is added to the cooled devolatilized polyester melt, before the so obtained mixture is solidified.
  • This embodiment is the same as the fifth particular preferred embodiment except that the devolatilized polyester melt obtained in step b) is not led through a static mixer, before it is led into the melt cooler.
  • the cyclic ester composition is subjected in step a) to a ring-opening-polymerization so as to obtain a crude polyester melt.
  • the ring-opening-polymerization step a) is performed at a temperature of 160 to 240°C and more preferably at a temperature of 170 to 210°C.
  • reaction time during the ring-opening- polymerization step a) is 0.5 to 3 hours and more preferably 1 to 2 hours.
  • the cyclic ester composition being subjected to the ring-opening polymerization comprises at least one catalyst or at least one catalyst is added to the cyclic ester composition before starting the ring-opening-polymerization step a) or at least one catalyst is added to the cyclic ester composition during the ring-opening- polymerization step a).
  • the presence of catalyst assists in the shortening of the required reaction time and of the required reaction tempera- ture.
  • suitable catalysts are metal oxides, metal carbonates, metal bicarbonates and organometallic compounds.
  • Suitable examples for metal oxides are transition metal oxides and suitable examples for organometallic compounds are those comprising a metal selected from the group consisting of magnesium, titanium, zinc, aluminum, indium, yttrium, tin, lead, antimony, bismuth and any combination of two or more of the aforementioned metals and an organic residue being selected from the group consisting of alkyl groups, aryl groups, halides, oxides, alkanoates, alkoxides and any combination of two or more of the aforementioned groups.
  • Suitable examples for metal carbonates and metal bicarbonates are alkali metal carbonates, alkaline earth metal carbonates, alkali metal bicarbonates and alkaline earth metal bicarbonates.
  • catalysts being selected from the group consisting of tin oxide, iron oxide, copper oxide, tin octanoate, butyl tin oxide, calcium carbonate, potassium carbonate and arbitrary combinations of two or more of the aforementioned catalysts.
  • the catalyst is tin octanoate (Sn(Oct)2).
  • the molar ratio of catalyst to cyclic ester being contained in the cyclic ester composition is more than 10,000 and more preferably 18,000 to 100,000.
  • the catalyst content in the cyclic ester composition being subjected to the ring-opening-polymerization step a) is 20 to 350 ppm and more preferably of 30 to 150 ppm.
  • the cyclic ester composition comprises at least one initiator or at least one initiator is added to the cyclic ester composition before starting the ring-opening- polymerization step a) or at least one initiator is added to cyclic ester composition during the ring-opening-polymerization step a).
  • the at least one initiator is preferably a hydroxy compound and more preferably a hydroxy compound being select- ed from the group consisting of monohydroxy compounds, dihydroxy compounds, trihydroxy compounds, tetrahydroxy compounds and any combination of two or more of the aforementioned compounds.
  • the functionality of the at least one hydroxy compound the design of the resulting copolymer can be adjusted. If a monohydroxy compound is used, a linear copolymer will be produced, whereas branched copolymers may be produced by using one or more dihydroxy compounds, trihydroxy compounds and/or tetrahydroxy compounds.
  • the at least one initiator is selected from the group consisting of 2-ethyl hexanol, 1 -decanol, Cio-C2o-monohydroxy fatty alcohols, benzyl alcohol, p-phenylbenzyl alcohol, ethylene glycol, propylene glycol, butane-1 ,4-diol, polyethylene glycol) with a weight average molecular weight of 200 to 10,000 g/mol, 2-hydroxymethyl-1 ,3-propane, glycerol, polyglycerol with a weight average molecular weight of 100 to 1 ,000 g/mol, trihydroxybenzene (phloroglucinol), trimethylolpropane and its dimer, pentaerythritol and its dimers and any combination of two or more of the aforementioned compounds.
  • the at least one initiator is selected from the group consisting of 2-ethyl hexanol, 1 -decanol, Cio-C2o-mon
  • the molar ratio of cyclic ester being contained in the cyclic ester composition to initiator is more than 100 to 10,000. More preferably, the molar ratio of cyclic ester being contained in the cyclic ester composition to initiator is 300 to 10,000, even more preferably 500 to 10,000 and most preferably 500 to 3,000.
  • the total amount of the at least one initiator applied during the ring-opening- polymerization may be also expressed as less than 0.1 to 50 meq or less than 0.1 to 50 mmol/kg, respectively, preferably 0.5 to 40 meq or mmol/kg, respectively, more preferably 1 to 30 meq or mmol/kg, respectively, and most preferably 1 to 20 meq or mmol/kg, respectively.
  • the present invention is not particularly limited concerning the kind of reactor, in which the ring-opening-polymerization step is performed.
  • a reactor system which comprises at least one continuous stirred-tank reactor, at least one loop reactor or, in series, a combination of at least one continuous stirred-tank reactor and at least one plug flow reactor, a combination of at least one loop reactor and at least one plug flow reactor or a combination of a continuous stirred-tank reactor, a loop reactor and a plug flow reactor.
  • the reactor if one reactor is comprised in the reactor system, or at least one and more preferably each of the reactors, if two or more reactors are comprised in the reactor system, in which the ring-opening-polymerization step is performed, comprises at least one mixer and/or at least one heat transfer element.
  • the reactor if one reactor is comprised in the reactor system, or at least one and more preferably each of the reactors, if two or more reactors are comprised in the reactor system, in which the ring-opening-polymerization step is performed, comprises at least one mixer and at least one heat transfer element.
  • the mixer may be a static mixer, such as of a type as described further above.
  • the mixer may be a dynamic mixer, i.e.
  • a mixer comprising moving and in particular rotating parts, for instance a dynamic mixer of the impeller-type, such as preferably a dynamic mixer comprising one or more paddle-type impellers, one or more anchor type-impellers, one or more gate-type impellers and/or one or more helical-type impellers.
  • a dynamic mixer of the impeller-type such as preferably a dynamic mixer comprising one or more paddle-type impellers, one or more anchor type-impellers, one or more gate-type impellers and/or one or more helical-type impellers.
  • the cyclic ester composition is purified, before it is subjected to the ring-opening- polymerization step a).
  • the purification of the cyclic ester composition may comprise at least one distillation step as well as one crystallization step. It has been found in the present invention that by performing the ring-opening reaction with a cyclic ester composition having been purified first by distillation and then by crystallization, the residence time or reaction time, respectively, of the ring- opening-polymerization of cyclic ester to polyester with a given molecular weight can be significantly reduced, namely from about 9 hours to about 2 to 3 hours.
  • this embodiment of the present invention allows to produce very pure polyester having a residual monomer content of as low as less than 0.1 % by weight.
  • this embodiment of the process in accordance with the present invention is characterized by a high single pass conversion.
  • the purification of the cyclic ester composition comprises at least one distillation step so as to obtain at least an overhead composition and a bottom composition and optionally at least one side composition as well as comprises at least one crystallization step of crystallizing the overhead composition, the bottom composition or the optional at least one side composition obtained in the at least one distillation step so as to obtain the purified cyclic ester composition, which is then subjected, optionally after adding catalyst and/or initiator as described above, to the ring-opening-polymerization.
  • the at least one crystallization step is a melt crystallization step, which means in accordance with the present invention a crystallization, which is performed from the melt of the cyclic ester composition containing at least one cyclic ester having been pre-purified in the at least one previous distillation step without addition of further components thereto, such as for examples solvents.
  • the at least one crystallization step may be performed in any manner, for example the at least one crystallization step may com- prise a static crystallization step or a dynamic crystallization step, for instance a falling film crystallization step or a suspension crystallization step.
  • the at least one crystallization step may comprise a combination of a static crystallization step followed by a dynamic crystallization step or a dynamic crystallization step followed by a static crystallization step.
  • the at least one crystallization step comprises at least one static crystallization step.
  • Static crystallization has the advantage that it economically purifies compounds, which are contained in the crystallization liquid in comparable high amounts.
  • the liquid phase is not moved and thus the crystals are formed and grown in a static liquid phase.
  • a typical static crystallizer comprises a plurality of walls, such as plates or tubes or finned tubes, which can be cooled and heated by circulating a heat transfer medium through the interior of the plates, wherein the crystals deposit at the cooled walls.
  • the at least one crystallization step comprises at least one dynamic crystallization step.
  • the liquid phase is moved in the crystallizer.
  • Prominent dynamic crystallization techniques are suspension crystallization and falling film crystallization. More specifically, during the suspension crystallization the cyclic ester composition having been pre-purified in the at least one previous distillation step is cooled in a vessel so that crystal particles being enriched in cyclic ester are formed so as to form a suspension, in which the crystal particles are dispersed in the liquid phase, which is depleted during the crystallization more and more concerning the cyclic ester so that the liquid phase is called after the start of the suspension crystallization mother liquid.
  • the crystal particles are separated from the mother liquid, e.g. by filters, centrifuges or other equipment for solid/liquid separation, and are then molten so as to obtain the purified cyclic ester composition.
  • falling film crystallization is performed in a falling film crystallizer, which is a crystallization column, which comprises hollow tubes being arranged at least substantially vertically and extending from the upper part of the falling film crystallizer into the bottom area of the falling film crystallizer. Cyclic ester composition is filled into the bottom area of the falling film crystallizer, before the crystallization process is started.
  • this cyclic ester composition is pumped by means of one or more pumps continuously from the bottom area of the falling film crystallizer to the upper part of the falling film crystallizer and is introduced into the upper end of the hollow tubes and allowed to fall down as falling film on the inner surfaces of the hollow tubes back to the bottom area of the falling film crystallizer.
  • the outer walls of the hollow tubes are cooled to a temperature below the equilibrium freezing temperature of the cyclic ester composition by allowing a cold heat transfer medium to flow as falling film down the outer surfaces of the hollow tubes so that crystal layers enriched in cyclic ester are deposited on the cooled inner wall surfaces of the hollow tubes.
  • a mother liquid is formed, which has a lower cyclic ester concentration than the cyclic ester composition.
  • the circulation of the mother liquid is conducted as long as necessary to separate the desired amount of cyclic ester from the mother liquid and to deposit it as crystals on the inner wall surfaces of the hollow tubes.
  • the mother liquid is completely removed from the falling film crystallizer, the cyclic ester crystal layers deposited on the inner wall surfaces of the hollow tubes are molten and then removed from the falling film crystallizer in order to obtain the purified cyclic ester composition.
  • Each of the aforementioned crystallization steps may be performed in one crystallization stage or, if the purity of the cyclic ester composition after one crystallization stage is not high enough, in multiple crystallization stages comprising two or more crystallization stages. If two crystallization stages are performed, the purified cyclic ester composition obtained after the first crystallization stage is fed as feed into a second crystallization stage and is crystallized there again so as to obtain crystal layers of further purified cyclic ester and mother liquid being depleted in cyclic ester, whereas the mother liquid obtained in the second crystallization stage is led into the first crystallization stage.
  • the purified cyclic ester composition obtained after the second crystallization stage is fed as feed into a third crystallization stage and is crystallized there again so as to obtain crystal layers of further purified cyclic ester and mother liquid being depleted in cyclic ester and so forth and so forth, whereas the mother liquid obtained in the third crystallization stage is led into the second crystallization stage and the mother liquid obtained in the second crystallization stage is led into the first crystallization stage.
  • the at least one crystallization step comprises one to ten crystallization stages, more preferably one to five crystallization stages, still more preferably one to three crystallization stages and most preferably two or three crystallization stages.
  • the process further comprises that at least one catalyst inhibitor is added to the crude polyester melt before starting the devolatilization in step b).
  • catalyst inhibitor is added to the cyclic ester composition, a degradation of the polyester by a backbiting reaction, i.e. the splitting off from a cyclic ester being formed by intramolecular esterification between the terminal carboxylic acid group of a terminal repeating unit and the ester group of an adjacent repeating unit from a polyester, thus leading to degraded polyester with reduced molecular weight, is reliably avoided.
  • the addition of a catalyst inhibitor to the cyclic ester composition is in particular advantageous, because the high temperatures of the subsequent devolatilization step favors back-biting reactions.
  • the at least one catalyst inhibitor is a phosphate ester or an alkyl phosphite. More preferably, the phosphate ester or alkyl phosphite has a total carbon number per molecule of 8 to 18. A sufficiently long carbon chain in the catalyst inhibitor leads to a low vaporization under devolatilization conditions, whereas a not too long carbon chain in the catalyst inhibitor assures that the melting point of the catalyst inhibitor is not too high, so that the catalyst inhibitor is a viscous liquid at room temperature.
  • Suitable examples for phosphate esters are phosphated alcohols, phosphated alcohol ethoxylates and phosphated phenol ethoxylates
  • suitable examples for alkyl phosphites are trioctyl phosphite, tri-isooctyl phosphite, tri-2-ethyl hexyl phosphite, trinonyl phosphite, triisodecyl phosphite, tri-lauryl phosphite, tricetyl phosphite and tristearyl phosphite.
  • the at least one catalyst inhibitor may be added to the crude polyester melt and mixed therewith using one or more mixers. All of the mixers mentioned above are also suitable as mixer for this embodiment.
  • 0.01 to 1% by weight and more preferably 0.5 to less than 0.1 % by weight of catalyst inhibitor are added to 100% by weight of crude polyester melt.
  • the devolatilization step b) is performed at a temperature of at least 200°C and at a pressure of less than 500 Pa in at least one devolatilization stage so as to obtain a gaseous composition and a devolatilized polyester melt.
  • the devolatilization may be performed in one devolatilization stage or in two or more subsequent devolatilization stages.
  • the devolatilization is performed in one to five, more preferably in one to four, still more preferably in one to three and most preferably in one or two devolatilization stages. If two or more devolatilization stages are performed, the crude polyester melt being devolatilized in the first devolatilization stage is fed into the second devolatilization stage and is devolatilized therein and is, if one or more further devolatilization stages are performed, fed into the next devolatilization stage.
  • the gaseous composition containing unreacted cyclic ester obtained in the one or more devolatilization stages is condensed to a liquid composition containing unreacted cyclic ester, wherein the liquid composition containing unreacted cyclic ester is at least partially recycled to the cyclic ester composition, before it is subjected to step a).
  • the gaseous composition or at least 50 to 90% by weight of the gaseous composition are recycled to the cyclic ester composition containing at least one cyclic ester.
  • the process further comprises a step d) of pelletizing the devolatilized polyester melt obtained in step c) to polyester pellets.
  • the devolatilized polyester melt may be led through a melt-cooler in order to facilitate the pelletization, for example as strand pelletization or as underwater pelletization.
  • the solid polyester composition contains, based on 100% by weight of the polyester composition, 70 to 99.99% by weight of polyester and 0.01 to 30% by weight of additive(s). Good results are in particular obtained, when the solid polyester composition contains, based on 100% by weight of the polyester composition, 90 to 99% by weight of polyester and 0.01 to 10% by weight of additive(s).
  • the single pass conversion of the process is preferably at least 95% and more preferably at least 98%.
  • the polyester contained in the solid polyester composition has a weight average molecular weight of more than 10,000 g/mol and more preferably a weight average molecular weight of 30,000 to 150,000 g/mol.
  • the number- and weight-average molecular weight (Mn and Mw) of polymers is determined by gel permeation chromatography using a poly(methyl methacrylate) standard and a sample concentration of 1 to 5 mg/ml in 1 ml HFIP depending on the sample’s molecular weight, wherein the column temperature is 40°C, the temperature of the Rl-Detector (refractive index) is 40 °C and the flow rate 1 ml/min.
  • the polydispersity i.e. the ratio of Mw/Mn, of the polyester contained in the solid polyester composition is at most 2. More preferably, the polydispersity of the polyester is 1 .0 to 1 .6 and most preferably 1.1 to 1 .4.
  • Fig. 1 shows a schematic view of a plant suitable for performing the process of producing a solid polyester composition in accordance with one embodiment of the present invention.
  • Fig. 3a to c show three embodiments for the possible additive addition before or in the devolatilization unit as alternatives to that embodiment of the plant shown in figure 1 .
  • Fig. 4a to c show four different types of static mixers one of which being also a heat transfer element useable in the process in accordance with the present invention.
  • the outlet line 42 for pre-purified cyclic ester composition of the crystallization unit 30 is combined with an inlet line 44 for catalyst, with an inlet line 46 for initiator and with an inlet line 48 for further additive and leads into an inlet of the polymerization reactor system 40, which comprises a mixer (not shown) and a heat transfer element (not shown) and which comprises an outlet line 52 for crude polyester melt. Furthermore, the outlet line 52 for crude polyester melt of the reactor system 40 is combined with an inlet line 54 for catalyst inhibitor and with an inlet line 54’ for further additive and leads into an inlet of the devolatilization unit 50.
  • the devolatilization unit 50 comprises an outlet and recycle line 58 for unreacted cyclic ester, which is connected with a condenser (not shown) and leads into the outlet line 32 of the distillation column 20 leading into the inlet of the crystallization unit 30.
  • the devolatilization unit 50 comprises an outlet line 56 for waste as well as an outlet line 62 for devolatilized polyester melt.
  • the outlet line 62 for devolatilized polyester melt of the devolatilization unit 50 is combined with an inlet line 64 for additive and leads into the pelletizing unit 60, which comprises an outlet line 66 for pellets made of polyester composition.
  • crude cyclic ester composition containing at least one cyclic ester is fed through line 22 into the distillation column 20, in which it is distilled. While lower boiling impurities are withdrawn from the distillation column 20 via the overhead outlet line 24 and higher boiling impurities are withdrawn from the distillation column 20 via the bottom outlet line 26, the pre-purified crude cyclic ester composition is withdrawn from the distillation column 20 via the side outlet line 32. The pre-purified crude cyclic ester composition is then mixed in the side outlet line 32 with the recycled condensed unreacted cyclic ester and is led into the crystallization unit 30, in which it is crystallized.
  • the purified cyclic ester composition is withdrawn from the crystallization unit 30 via the outlet line 42, wherein catalyst, initiator and further additive is added thereto via the inlet lines 44, 46, 48, before the so obtained mixture is led into the polymerization reactor system 40, in which it is mixed to a homogenous mixture and subjected to a ring-opening- polymerization reaction so as to obtain a crude polyester melt.
  • the crude polyester melt is then led via line 52, while catalyst inhibitor and further additive are added thereto via the inlet lines 54, 54’, into the devolatilization unit 50, in which the crude polyester melt is separated into i) waste being withdrawn via the outlet line 56, into ii) unreacted cyclic ester being withdrawn via the outlet and recycle line 58 as well as being condensed and recycled into line 32, as well as into iii) devolatilized polyester melt, which is withdrawn from the devolatilization unit 50 via the outlet line 62.
  • FIGS. 2a to 2d show four different embodiments concerning the possible additive addition between the devolatilization unit 50 and the pelletizing unit 60 of the plant 10 shown in figure 1 . More specifically, the outlet line 62 for devolatilized polyester melt as well as the inlet line 64 for additive lead in the embodiment shown in figure 2a through a static mixer 68 and downwards thereof through a melt cooler 70, before it enters into the pelletizing unit 60.
  • the devolatilized polyester melt being withdrawn from the devolatilization unit 50 is led into the static mixer 68, in which it is contacted and mixed with the additive being fed into the static mixer 68 via the inlet line 64 for additive, before the mixture being obtained in the static mixer 68 is led into the melt cooler 70, in which the mixture is cooled, but not solidified, before the cooled, but not solidified mixture is fed into the pelletizing unit 60, in which it is pelletized to pellets of the polyester composition.
  • the outlet line 62 for devolatilized polyester melt also leads through a static mixer 68 and downwards thereof through a melt cooler 70, before it enters into the pelletizing unit 60.
  • an extruder 72 is present, into which the inlet line 64 for additive leads and from which an extruder outlet line 74 leads into the static mixer 68.
  • This embodiment is particularly suitable for the addition of solid additive.
  • the devolatilized polyester melt being withdrawn from the devolatilization unit 50 is led via line 62 into the static mixer 68.
  • Solid additive is led via line 64 into the extruder 72 and is molten therein, before the molten additive is led via the extruder outlet line 74 into the static mixer 68, in which it is contacted and mixed with the devolatilized polyester melt, before the mixture being obtained in the static mixer 68 is led into the melt cooler 70, in which the mixture is cooled, but not solidified, before the cooled, but not solidified mixture is fed into the pelletizing unit 60, in which it is pelletized to pellets of the polyester composition.
  • the embodiment shown in figure 2c correspond to that shown in figure 2b, except that in addition an inlet line 76 for solid polymer leads into the extruder 72. This embodiment is particularly suitable for the addition of solid and heat sensitive additive.
  • the devolatilized polyester melt being withdrawn from the devolatilization unit 50 is led via line 62 into the static mixer 68.
  • Solid additive is led via line 64 into the extruder 72 and solid polymer, which may be for instance a portion of the polyester pellets being withdrawn from the plant 10 via the outlet line 66, is led via inlet line 76 into the extruder 72, in which the additive and the polymer are molten and mixed with each other.
  • the mixture being obtained in the extruder 72 is led via the extruder outlet line 74 into the static mixer 68, in which it is contacted and mixed with the devolatilized polyester melt, before the mixture being obtained in the static mixer 68 is led into the melt cooler 70, in which the mixture is cooled, but not solidified, before the cooled, but not solidified mixture is fed into the pelletizing unit 60, in which it is pelletized to pellets of the polyester composition.
  • the embodiment shown in figure 2d correspond to that shown in figure 2c, except that the extruder outlet line 74 does not lead into the static mixer 68, but into line 62 between the melt cooler 70 and the pelletizing unit 60.
  • the devolatilized polyester melt being withdrawn from the devolatilization unit 50 is led via line 62 through the static mixer 68 and through the melt cooler 70, in which it is cooled, but not solidified.
  • Solid additive is led via line 64 into the extruder 72 and solid polymer, which may be for instance a portion of the polyester pellets being withdrawn from the plant 10 via the outlet line 66, is led via inlet line 76 into the extruder 72, in which the additive and the polymer are molten and mixed with each other.
  • the melt mixture being obtained in the extruder 72 is led via the extruder outlet line 74 into line 62, in which it is contacted and mixed with the cooled, but not solidified devolatilized polyester melt, before the so obtained mixture is fed into the pelletizing unit 60, in which it is pelletized to pellets of the polyester composition.
  • Figures 3a to 3c show three embodiments for the possible additive addition before or in the devolatilization unit 50 as alternatives to that embodiment of the plant 10 shown in figure 1 . More specifically, in difference to the embodiment shown in figure 1 , the inlet line 54’ for further additive leads in the embodiment shown in figure 3a into an extruder 72, from which an outlet line 74 leads into the outlet line 52 for crude polyester melt, before line 52 leads into the devolatilization unit 50.
  • additive in particular solid additive
  • line 54’ additive, in particular solid additive, is led through line 54’ into the extruder 72, in which it is molten and homogenized, before the additive melt is led via line 74 into line 52, where the additive melt is mixed with the crude polyester melt, before the so obtained mixture is led into the devolatilization unit 50.
  • the embodiment shown in figure 3b differs from that shown in figure 1 in that the devolatilization unit 50 comprises two devolatilization stages 51 , 5T, which are connected with each other by a line 62’ for devolatilized polyester melt.
  • Both devolatilization stages 51 , 5T comprises an outlet and recycle line 58, 58’ for unreacted cyclic ester, which are both connected with each other.
  • both devolatilization stages 51 , 5T comprises an outlet line 56, 56’ for waste, which are both connected with each other.
  • the inlet line 54’ for further additive does not lead into the outlet line 52 upstream of the devolatilization unit 50, but into the line 62’ for devolatilized polyester melt connecting the first devolatilization stage 51 and the second devolatilization stage 5T.
  • additive in particular liquid additive, is led through line 54’ into line 62’, where the additive is mixed with the devolatilized polyester melt being obtained in the first devolatilization stage 51 , before the so obtained mixture is led into the second devolatilization stage 5T.
  • the embodiment shown in figure 3c differs from that of figure 3b in that the inlet line 54’ for further additive leads into an extruder 72, from which an outlet line 74 leads into the line 62’ for devolatilized polyester melt connecting the first devolatilization stage 51 and the second devolatilization stage 5T.
  • additive in particular solid additive
  • line 54’ into the extruder 72, in which it is molten and homogenized, before the additive melt is led via line 74 into line 62’, where the additive melt is mixed with the devolatilized polyester melt being obtained in the first devolatilization stage 51 , before the so obtained mixture is led into the second devolatilization stage 5T.
  • Figure 4 shows three different types of static mixers useable in the method in accordance with the present invention, namely in figure 4a a static mixer 82 of the x-type comprising deflection means 84 in the form of crossbars having in a plan view as well as in side view a x-like form.
  • Figure 4b shows a static mixer 82 of the baffle plate-type comprising longitudinal deflection means 84.
  • Figure 4c shows a combined static mixer and heat transfer element 26 with tube-like deflection means 84 being formed so that they function as heat transfer element by transporting heat transfer medium within the tubes and simultaneously as static mixer for liquid being transported outside of the tube-like deflection means 84, such as it is commercially distributed by Sulzer Chemtech Ltd under the tradename SMR.
  • a miniextruder (72) was used to mix and dose a 10:1 mixture of neat polycaprolactone (76) and Irganox (64) into the system (as in-situ masterbatch), giving an ultimate Irganox weight loading of 0.1 %.
  • This “masterbatch” was then mixed with the mainstream (62) through a static mixer (68) prior to entering the melt cooler (70), water bath, and finally be pelletized (60).
  • the molecular weight of the polymer melt at different stages are shown in table 1 .
  • the above example was repeated without dosing Irganox.
  • the polymer melt was cooled down in a water bath and pelletized, it was dried at 50°C in dry air for 2 h and stored in a sealed package kept inert atmosphere. Afterwards, the pellets were extruded with heating zones ranging from 50 to 160°C and a rotational speed of 300 rpm. Irganox was then dosed at a rate to target a final composition of 0.1 %.
  • the molecular weight of the polymer was measured by gel permeation chromatography (GPC) and the results are summarized in the table 1 .
  • Table 1 Number average molecular weight of polycaprolactone at different stages of processing.
  • Outlet line for crude polyester melt Inlet line for catalyst inhibitor ’ Inlet line for further additive , 56’ Outlet line for waste , 58’ Outlet and recycle line for unreacted cyclic ester Pelletizing unit , 62’ Outlet line for devolatilized polyester melt
  • Static mixer Melt cooler Extruder Extruder outlet line Inlet line for solid polymer Static mixer and heat transfer elements Static mixer Deflection means

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

La présente invention concerne un procédé de production d'une composition de polyester solide contenant un additif à partir d'une composition d'ester cyclique contenant au moins un ester cyclique comprenant les étapes consistant à : a) polymériser le ou les esters cycliques contenus dans la composition d'ester cyclique par polymérisation par ouverture de cycle de manière à obtenir une masse fondue de polyester brute, b) dévolatiliser la masse fondue de polyester brut de façon à obtenir une composition gazeuse et une masse fondue de polyester dévolatilisée et c) post-traiter la masse fondue de polyester dévolatilisée de façon à obtenir une composition de polyester solide, au moins un additif et au moins un polyester solide étant introduits dans une extrudeuse et étant mélangés, avant que le mélange ainsi obtenu ne soit ajouté avant ou pendant l'étape a) dans la composition d'ester cyclique ou après l'étape a) dans la masse fondue de polyester brute ou dans la masse fondue de polyester dévolatilisée.
PCT/EP2025/070179 2024-07-16 2025-07-15 Procédé de production efficace d'une composition de polyester solide contenant un additif Pending WO2026017663A1 (fr)

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Citations (11)

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US3743250A (en) 1972-05-12 1973-07-03 E Fitzhugh Fluid blending device to impart spiral axial flow with no moving parts
EP0655275B1 (fr) 1993-11-26 1999-10-06 Sulzer Chemtech AG Dispositif de mélange statique
EP0815929B1 (fr) 1996-07-05 2000-08-30 Sulzer Chemtech AG Mélangeur statique
EP1206962A1 (fr) 2000-11-17 2002-05-22 Sulzer Chemtech AG Mélangeur statique
WO2010066457A1 (fr) 2008-12-10 2010-06-17 Technische Universiteit Eindhoven Mélangeur statique équipé d'un élément de mélange statique, procédé de mélange d'un fluide dans un canal, et formule permettant de concevoir cet élément de mélange statique
EP2158027B1 (fr) 2007-06-22 2011-11-09 Sulzer Chemtech AG Élément de mélange statique
EP2548634B1 (fr) 2011-07-22 2014-08-06 Sulzer Mixpac AG Elément de mélange pour mélangeur statique
US20160280908A1 (en) * 2013-11-20 2016-09-29 Uhde Inventa-Fischer Gmbh Process and apparatus for preparation of a crystallizable polylactic acid mixture, and polylactic acid mixture
CN107099872A (zh) * 2017-06-02 2017-08-29 苏州宇希新材料科技有限公司 一种环保型新材料聚乳酸纤维制备方法
CN114573797A (zh) * 2022-04-01 2022-06-03 温州邦鹿化工有限公司 一种丙交酯生产聚乳酸切片连续聚合工艺
CN116217900A (zh) * 2021-12-02 2023-06-06 惠生工程（中国）有限公司 一种乙交酯、丙交酯开环共聚合制备pgla的装置及工艺

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3743250A (en) 1972-05-12 1973-07-03 E Fitzhugh Fluid blending device to impart spiral axial flow with no moving parts
EP0655275B1 (fr) 1993-11-26 1999-10-06 Sulzer Chemtech AG Dispositif de mélange statique
EP0815929B1 (fr) 1996-07-05 2000-08-30 Sulzer Chemtech AG Mélangeur statique
EP1206962A1 (fr) 2000-11-17 2002-05-22 Sulzer Chemtech AG Mélangeur statique
EP2158027B1 (fr) 2007-06-22 2011-11-09 Sulzer Chemtech AG Élément de mélange statique
WO2010066457A1 (fr) 2008-12-10 2010-06-17 Technische Universiteit Eindhoven Mélangeur statique équipé d'un élément de mélange statique, procédé de mélange d'un fluide dans un canal, et formule permettant de concevoir cet élément de mélange statique
EP2548634B1 (fr) 2011-07-22 2014-08-06 Sulzer Mixpac AG Elément de mélange pour mélangeur statique
US20160280908A1 (en) * 2013-11-20 2016-09-29 Uhde Inventa-Fischer Gmbh Process and apparatus for preparation of a crystallizable polylactic acid mixture, and polylactic acid mixture
CN107099872A (zh) * 2017-06-02 2017-08-29 苏州宇希新材料科技有限公司 一种环保型新材料聚乳酸纤维制备方法
CN116217900A (zh) * 2021-12-02 2023-06-06 惠生工程（中国）有限公司 一种乙交酯、丙交酯开环共聚合制备pgla的装置及工艺
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